Manufacture of primary cells



"1;402,2 5, Patented Jan. 3, 192? 'H; 0E OLANETA. MANUFACTURE OF PRIMARYCELLS.

APPLICATION FILED NOV. 26. 1919.

V 4 21 (fl Norma Q tamed in a paste or.

i To all whom it may concern:

or contain among other pyrolusite,

' present application is a. division.

HAROLD DE OLANETA, onNEw REPEATINGARMS COMPANY,

CONNECTICUT.

Oi'iginaI application filed May 24',

Be it known that I, HARoLn DE O ANErA, a citizen of the United States,residlng 1 n New Haven, New Haven county, Connecticut, haveinventedcertaiu new and useful- Improvements in'the Manufacture ofPrimary Cells, ofwhich the followin is a full, clear, and exactdescription v 1 This invention relates to the manufacture of primarycells. It pertains more especially to small dry cells such aS those usedinconnection with pocket flash-lights, -where manganiferous material isused as a depolarizing agent, and 'where the exciting solution, e. g.,

a solution of ammonium chloridwith or without zinc chlorid, is carriedby or congelatinous substance.

- The invention is not limited,.however, to this particular application.

My present invention has particular ref-J purification of the depolarizerence to the ing material prior to its incorporation in the cell.

ganese generically designated as manganese dioxid. The manganesematerial may be things comminuted or manganese ore, an artificial orrecovered manganese dioxid produced by hydration, or a precipitate ofmanganese, as described in my application Serial No. 299,522, filed May24,-191'9, of whiph tge n t e following description Ishall assume, for

purposes of explanation only, ization is to be effected by or with asuitable manganlferous that depolarmaterial havmg or susceptible oftaking up a'high content of .oxvgen for combination or'other coactionwith the hydrogen which is liberated 'in the cell.

The manganese dioxid commonly used in dry cellsc'ontains in many cases anumber of impurities which have a on thecell and shortens its life. Iascribe this toijthe fact that the impurities are acted upon by orsoluble in the electrolyte, e. g.,sal ammoniac solution, with the resultthat as 'soon as. the ordinary cell is made, a local Specification ofLetters Patent. 7

quantity, the cell .way to the zinc,

The depolarizer may consist of depending on the or comprise one or morecompounds of manin connection.

invention deleterious action HAVEN, CONNECTICUT, ASSIGNOR ITO WINCH STERon NEW HAVEN, CONNECTICUT, A CORPORATION or MANUFACTURE OF IjRIMARYCELLS.

, action is set up which short-circuits the cell PatentedJan. 3,1922. 119, Serial No. 299,522: Divided and this application filed Noveni- 'bel2c, 1919. Serial No. 340,752. I v

for example, iron is present in a substantial I will be drained in avery short time, because the iron is converted into an oxid of iron,which eventually finds its and once in contact with the zinc a. localaction is setup. If, for further example, potash of any description,either free or neutralized, is present in .the manganese dioxid, the sal ammoniac will dissolve the same and form a" salt with the zinc or withany zinc salt present, setting up a deleterious local action. Thesedeleterious substances in the manganese often include iron, copper andphosphorus, when manganese ore or pyrolusite is used. WVhen artificialor hydrated manganese dioxid is employed, sulphur, oxids, nitrates, orchlorids will often be found,

process of hydration;

potash or the like will be impurities, and

others, when chemically combined with the manganese, are insoluble inwater, and when it is attempted to separate them out by the use ofacids, for example, the result will either be .that the manganese isdissolved, on the one hand, or, on the. other insoluble compounds arecreated.

'One of the primary objects of the present is to furnish an improvedprocess for the manufacture of a relatively cheap but extremelyeflicient and satisfactory depolarizing material for primary cells, andmore particularly small dry cells.

Another objectv of my in thoseimpurities or substances 'in thefdepolarizer which set up local action Ord a te other deleterious effectsas a result of dissolutionin or action on the electrolyte while the cellis not in use are eliminated priorto the assembly of the cell parts.

hand, that 9b invention is to provide aamethod of manufacturing cellswhere of the cell, with a solution containing one or more of the saltsused in" the excitin solution or paste of the battery (and pre erably.of approximately the same concentration),

whereby all deleterious impurities s'olublein the exciter areremovedgprior to the-assembl of the cell.

' ore specifically, in the improvement in the manufacture of drylcellshaving a. manganiferous depolarizer, which resides certain procedureprek liminary "to the assembly ofthe cell, that is calculated to preventaction of the sal ammoniac on the manganiferous materialwhile the cellis on the shelf.

B my invention I also make itpossible commercially to utilize forbattery manuj,facture, and more' especially for use as a 'fdep'olarizer,certain manganiferousmaterials which have hitherto not 'fully in thisart.

been used success The invention also consists in other novel "featureshereinafter described and claimed.

The accompanying drawing shows a dia grammatic sectional view of a drycell of one typein connection with'which my 1nvention maybe carried intoeflect.

In carrying out eating themannerin which the invention my process, Iprefer to make 'use of a suitable tank of any appro riatesize, shape andmaterial, provided wit 2a perforated or screenlike bottom. On

. the bottom of the tank is placed a suitable piece of filteringmaterial, such as cloth. The manganese compound which is to be mployed,after having been ground' or comminuted, and sifted, is charged into thetank, leavin a certain amount of space at the top. solution of a neutralsalt usually an ammonium salt, for. e ample, a

- is then poured into the top of t so1ution.of -ammoni'um chlorid, 0 anyappropriate density, say, one degree Baum,

e tank onto the material andpermitted "to fpercolate through it; If itbeassumed that the manganese material takes up, say, two-thirds of thetank capacity,'the remaining on third of the tank will be filled withthesaline'solution, which 'will'pas s completely into the material undertreatment. in, say, twentyfour hours. Another-similar quantity of'thequantity of solution will be poured into' solution will then be pouredinto the tank and allowed to pass downinto the material in; the samemanner. vAfter the lapse of forty-eight hours, for example, a third thetank, and similar quantities of solution will be poured in at aproximately equal" hen the solution,

intervals, as needed.

my invention consiststom of the tank correspon .in at the top.

commences to. out of the tank at the bottom, the same is tested in anysuitable manner which permits comparison with the solution being pouredin at the top; I test and a decrease of density isnoted, until thesolution coming out of the bottom of ethe tank has the 'samedensity asthat pouredin at the top.- .No furtherlte'sts are then needed; When thematerial-being treated ispyrolusite, or natural manganese dioxid,

for exam 'Ie, the solution passin'goutat the b0tt0m,i its shows nodifierence in Baum;

is. tested chemically, which will indicate. the

character and amount of impurities, such as metallic oxids, which arebeing leached out. In any case, if the best results are to be obtained,the solution is passed through the material until that flowin out at thebotto that poured In" this process; which will consume a variable lengthof time, depending on the. kind of material treated, and the facilitiesavailable, the impurities in the material I shall now describe; oneexample indiwhich are soluble in the solution to be used in theassembled battery has an exciting he material remaining in the tank,

which is practically pure manganese oxids, 1s then taken out and driedand, if intended for use as a'dep'olarizing material, is permitted totake up oxygen from the air. 'The amount of oxygen absorbed will, ofcourse,

depend to a certain extent on the amount of the lower oxids of manganesecontained in the. initial material. When the impuris ties have beenremoved, the material will tendto absorb oxygen up to its fulloxygenabsorbing. capacity. It is preferable to expose the pu'rifiedmaterial to the air forse'veral: days at least, so that a maximum amountof oxygen will be taken up thereby before it is used'in the battery 'as'adepolarizer. w a

In .carrying'outv my vp ro cess,.I prefer to agent, and especially thosewhich render use a manganese precipitate as a starting material, or anycheap waste material con- I taining manganese,'but it will be understoodfrom what, has'been said above that the process can be carried outsuccessfully with more expensive grades of manganese;

One of the particular advantages of my process, however, consists in thefact that i very cheap manganese containing materials,

heretofore considered waste products, may be treated successfully andeconomically,

feriordepolar-izers now used.-

y my invention, very low grade material can beeasily and economicallyconverted into a high grade material which gives the very best resultsin the cell, increasing the E. M.

. F., and at the same time lengthening the life very considerably. Thepurified manganese material absorbs oxygen by a natural process, whichis not only very inexpensive as compared to hydration and similarprocesses, but the product, containing substantially nothing butmanganese and oxygen, and being in fact a very pure manganese dioxid,has much' greater depolarizing efiiciency than the substances commonlyemployed. The fact thatthe tests during the process of purificationindicate that the ammonium chlorid' used in the cell as an excitingagent will have no chemical eflect upon the depolarizer, is also animportant feature of advantage, as in this manner the possibility, ofany local-action being set up from thissource, is eliminated.

Obviously, the lowering of the cost of dry cells, by the use of lowgrade manganesecontainlng material, is a factor of no small importance.For example, I am able to use with entire success manganese compoundscomm'only occurring as waste products in the manufacture ofpermanganates, such as sodium permanganate, potassium permanganate andbarium permanganate. In the oxidizing of manganates to produce suchpermanganates, there are precipitations of manganese compounds which canbe purified to advantage by the above mentioned, process for theproduction of a very satisfactory depolarizer. Other products which canbe used" are precipitations formed by agents used to remove the oxygenfrom permanganates.

\Vhen oxygen is eliminated from a permanganate, for the purpose, say, ofoxidizing, a precipitate is thrown down which has heretofore beenconsidered practically worthless. If, however, the method previouslydescribed is used for the purification of a precipitate of this kind, itis a simple matter to recover all of the manganese. The impurities willbe largely dissolved. and removed by the ammonium salt in the mannerpreviously described, and the resulting pure manganese material willtake up oxygen, as above set forth, creating a manganese dioxid, whichis very desirable for battery use. Cells made up with thismaterial,showed on. current tests, approximatel 100% more lifethanstandard cells of similar'weight found on the market. 1

An example of a precipitate such as'that above indicated would be aresidue of potassome industrial floxidizing process, which residue 1sthrown down as abasis manganese nitrate or sulphate, for example. Thisma-' terial is so finely divided as'to be impalpable and usually has adarkblue color.

It is not necessary in all cases to expose such material to the airsubsequent toits treatment by my purification process (with a neutralsaline solution), for oxidation purposes, inasmuch as, with theimpurities such as potash eliminated, it --is exceptionally greedy intaking up oxygen from any available source, and the. necessary oxygenfor high oxidation is furnished it either from the substances usedinmixing up the' depolarizer cartridge or is material is brought intocontact with the electrolyte, .on putting together the parts of thecell. H

In my process above described, the densit of the solution poured intothe tank at various times should always be the same. That is, if I startout with a solution of one degree Baum, subsequent quantities of thesolution used are likewise not necessary to remove all of the salammoniac from the material before drying and oxidizing, if the materialis. to be used as a depolarizer. While it' is possible to remove the salammoniac by washing with water, the material, as I employ it for batterypurposes, carries a trace of sal ammoniac whenplaced in the cell. a r

In the drawing I have-showna sectional enlargement of a pocket dry cellin connection with the manufactureof which my in.- vention has beenpractised with very good results. In this drawing, 1 denotes a zinc cupwhich serves one electrode, and 2, a carbon rod serving as the otherelectrode. The depolarizing material, which may contain otheringredients in addition to the manganiferous material hereinbeforementioned,'is packed or rammed about the car bonelectrode in such amanner as to form a.

however, from what has been said above, that it is not essential in allcases to have the same kind of solution with which the depolarizingmaterial is treated for the removal of impurities, present later on in apaste within the cell, for while the invention has resulted I in amarked increase in the efficiency of cells of this type, other types maybe used.

taken up when the cartridge 3 covered with cheese-cloth or like iVarious changes and modifications may "be made in the detailedprocedure, and in other matters, without departing from the rial whichcomprises treatment of the .mate

rial. with a solution of a neutral salt, as claimed in my priorapplication hereinbefore identified, Neither do I claim herein. thenewdepolarizer for electric dry cells or the method of making the same, orof making a cell containing a depolarizer around the carbon electrode,eomprising recovered manganese or, more part cularly, a mangar'i atederivative, as claimed in'myapplicar.

tion Serial No. 360,353; nor do I claim the dry cell per se as claimedin my application Serial No. 378,456. -What I claimis: v 1. The methodof making a primary cell, having a depolarizer, which comprises'treateing the depolarizer material, prior to;the assembly ofthe cell,with. asolution containingone or more of the salts used in the elec-- trolyt'e,wherebydeleterious substances soluble in the electrolyte are removedbefore the cell is assembled;

2. The method (if-"making a primarycell having a depola'rizer' andganlelectrolyte, which COIDPIISGSI treatment "of 'the 'depolarizer withelectrolyte material prior to the assembly of the cell for removingimpurities that are soluble in'the electrolyte.

- 3. The method of makinga primary cell having a depolarizeianjd anelectrolyte,

which comprises as a p'relimin'ary step the leaching of the depolarizer.with; a solution containing electrolyte material prior to theassembly'of the cell.

' 4 The method of making a primary cell having a depolarizer and anelectrolyte, such electrolyte consistingof or containing a -ne'u-. tralsalt, which comprises; the treatment of the depolarizer' material riortthe incorporation of, the depolarizer in-thej cell, with asolution'containing such neutral salt.

5. The method ofsmaki'ng a primary cell having a depolarizepandanelectr0lyte,"sucl1.

electrolyteeonsisting of or containing a neutraltsalt,whiclrcomppisesthe treatment of the "dep olarizer 'mater a1 prior to the incorporationof the'dep'olarizer in the cell, with a solution containing such neutralsalt, such broadly herein a process consists inleaching treatment beingin the nature of lixiviation and being continued until substantially allsubstances in the depolarizer soluble in the electrolyte are eliminated.a i

6. The method of making a primary cell having a depolarizer and anelectrolyte, which comprises leaching the de olarizing material with asolution of electro yte material prior to the assembly of the cell, suchsolution of electrolyte material being of approximately the sameconcentration as the electrolyte.

7. In the'manufacture of primary cells, having a manganiferousdepolarizer, the treatment of the manganiferous material preliminary toits incorporation in the cell with a solution containing one or'more ofthe ingredients of the electrolyte to be used in the cell, whereby thesoluble impurities whose presence in the cell is deleterious to the lifeand strength thereof are removed before the cell is put together.

8. The method of making a primary cell:

having a manganiferous depolarizer, which 3 I with a neutral solvent."

9."The method'of manufacturing 'a-primary cell having a manganiferousdepolarizer and anelectrolyte consisting of or containing aneutral salt,which consists. in

leaching the manganiferous material prior the manganiferousma-J Ivterial prior to its incorporation in the'cell to its incorporation inthe cell with "asolu? I I tion' of such neutral salt. v

makinga primary cell having a mangamferous depolarizer and an 10. Themethod of electrolyte consistingof or contain ng a hentral ammoniumsalt, which consists in so;

treating the mangani ferous; 1 material, prior to the assembly of thecell, with such neutral. I

salt that impurities in' the depolarizeron which such salt would :actwhile the-cell is onthe shelf are eliminated before the parts of thecell are assembled.

11. The method of making a dry cell hav- I ing a imanganiferousdepolarizer, a pastein proximity thereto, and a saline exciting scilution in the paste, which comprises the leaching of the manganiferousmaterial with a quantity of such saline solution prior to the1 jincorporation. of such material in the The method'of making a dry cellhav- .iiiga depolarizer of manganiferous' mate rial, a paste inproximity thereto, anda solution of ammoniun'rchlorid in, the paste-,;which comprises the leachin ""ganiferous material with a so utioncontain ing ammonium chlorid but devoid of acid for-the removal ofimpurities soluble-in an ammonium chlorid solution.

13. The method of making a dry cell having adepolarizer, a paste anda'saline exciting. agent in the paste, which comprises the of. the man-ri treatment of the depolarizing material with a neutral salinesubstance, in the absence of acid, for the purpose ofremoving'deleteri-- ous substances.

14; In the manufacture of primary cells b wherein ammonium chlorid isused as an exc ting agent and a manganese 031d 1s employed as adepolarizer, leachlng the manganiferous material with asolution for theremoval of impurities, and exposing the re- 10 suiting depolarizingmaterial to the air for oxidation prior tothe assembly of the cell.

In witness whereof, I have hereunto set myhand on theQAth day ofNovember, 1919.

- HAROLD 1m OLANE'IA.

